CN111244295B - Quantum dot light-emitting diode and preparation method thereof - Google Patents
Quantum dot light-emitting diode and preparation method thereof Download PDFInfo
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- CN111244295B CN111244295B CN201811432412.7A CN201811432412A CN111244295B CN 111244295 B CN111244295 B CN 111244295B CN 201811432412 A CN201811432412 A CN 201811432412A CN 111244295 B CN111244295 B CN 111244295B
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- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
- H10K50/165—Electron transporting layers comprising dopants
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/10—Transparent electrodes, e.g. using graphene
- H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
- H10K2102/102—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising tin oxides, e.g. fluorine-doped SnO2
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
- H10K50/157—Hole transporting layers between the light-emitting layer and the cathode
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Abstract
The invention discloses a quantum dot light-emitting diode and a preparation method thereof, wherein the quantum dot light-emitting diode comprises a cathode, an anode and a quantum dot light-emitting layer arranged between the cathode and the anode, an electron transport layer is also arranged between the cathode and the quantum dot light-emitting layer, and the electron transport layer is made of a mixed material consisting of PAMAM dendrimer and nano metal oxide. The PAMAM dendrimer is a sigma donor and a pi donor, so that the PAMAM dendrimer has certain electron transport capacity, but the PAMAM dendrimer does not have free electrons per se, so that the electron transport capacity of the PAMAM dendrimer is weaker than that of a metal oxide. The mixed material composed of PAMAM dendrimer and nano metal oxide is used as the electron transport layer material, so that the electron mobility of the quantum dot light-emitting diode can be reduced, the electron hole injection rate of the quantum dot light-emitting diode is balanced, and the light-emitting efficiency of the quantum dot light-emitting diode is improved.
Description
Technical Field
The invention relates to the field of quantum dot light-emitting diodes, in particular to a quantum dot light-emitting diode and a preparation method thereof.
Background
The quantum dot light emitting diode is an important new display technology in the future, and the commercialization of the quantum dot display technology still has many technical problems, such as unstable device efficiency, poor lifetime, etc., and the main factor influencing the devices is caused by unbalanced charge injection of the devices.
For example, when a light emitting diode (QLED) is manufactured by using quantum dots of different structural systems in the same device structure, the device efficiency and the lifetime are different, because the quantum dots of different structural systems have different requirements for electron hole injection balance, and thus, the charge injection balance of the device needs to be adjusted and optimized.
For example, when quantum dots of the same structure system are used for manufacturing quantum dot light emitting diodes (QLEDs) by using different device structures, the device efficiency and the lifetime are different due to the different device structures, because the electron hole injection balance is not uniform due to the different device structures, the charge injection balance also needs to be adjusted and optimized for the different device structures.
Aiming at the problem of unbalanced charge injection of quantum dots of different structural systems under the same device structure and different device structures of quantum dots of the same structural system, the corresponding technology is still to be improved and developed.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, the present invention aims to provide a quantum dot light emitting diode and a method for manufacturing the same, which aims to solve the problem of low light emitting efficiency caused by unbalanced charge injection of the conventional quantum dot light emitting diode.
The technical scheme of the invention is as follows:
a quantum dot light-emitting diode comprises a cathode, an anode and a quantum dot light-emitting layer arranged between the cathode and the anode, wherein an electron transport layer is further arranged between the cathode and the quantum dot light-emitting layer, and the electron transport layer is made of a mixed material composed of PAMAM dendrimer and nano metal oxide.
A preparation method of a quantum dot light-emitting diode comprises the following steps:
providing an anode substrate, preparing a quantum dot light-emitting layer on the anode substrate, preparing an electron transport layer on the quantum dot light-emitting layer, and preparing a cathode on the electron transport layer to prepare the quantum dot light-emitting diode;
or, providing a cathode substrate, preparing an electron transport layer on the cathode substrate, preparing a quantum dot light-emitting layer on the electron transport layer, and preparing an anode on the quantum dot light-emitting layer to obtain the quantum dot light-emitting diode;
the electron transport layer material is a mixed material composed of PAMAM dendrimer and nano metal oxide.
Has the advantages that: the quantum dot light-emitting diode provided by the invention comprises an electron transport layer, wherein the electron transport layer is made of a mixed material consisting of PAMAM dendrimer and nano metal oxide. The PAMAM dendrimer is a sigma donor and a pi donor, so that the PAMAM dendrimer has certain electron transport capacity, but the PAMAM dendrimer does not have free electrons per se, so that the electron transport capacity of the PAMAM dendrimer is weaker than that of a metal oxide. The mixed material composed of PAMAM dendrimer and nano metal oxide is used as the electron transport layer material, so that the electron mobility of the quantum dot light-emitting diode can be reduced, the electron hole injection rate of the quantum dot light-emitting diode is balanced, and the light-emitting efficiency of the quantum dot light-emitting diode is improved.
Drawings
Fig. 1 is a schematic structural diagram of a quantum dot light emitting diode according to a preferred embodiment of the invention.
Fig. 2 is a schematic structural diagram of another quantum dot light-emitting diode according to a preferred embodiment of the invention.
Detailed Description
The invention provides a quantum dot light-emitting diode and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The quantum dot light-emitting diode has various forms, and the quantum dot light-emitting diode is divided into a formal structure and a trans structure, and the quantum dot light-emitting diode with the trans structure can comprise a substrate, a cathode, an electron transmission layer, a quantum dot light-emitting layer and an anode which are stacked from bottom to top. The embodiments of the present invention will be described mainly by taking quantum dot light emitting diodes with formal structures as shown in fig. 1 as examples. Specifically, as shown in fig. 1, the quantum dot light emitting diode with the formal structure includes a substrate 10, an anode 20, a quantum dot light emitting layer 30, an electron transport layer 40, and a cathode 50, which are stacked from bottom to top, wherein the electron transport layer is made of a mixed material composed of PAMAM dendrimer and nano metal oxide.
For the quantum dot light-emitting diode with the formal structure and the trans-structure, a hole functional layer such as a hole transport layer, a hole injection layer and an electron blocking layer can be arranged between the anode and the quantum dot light-emitting layer; besides the electron transport layer, an electron injection layer, a hole blocking layer and other electronic functional layers can be arranged between the cathode and the quantum dot light-emitting layer.
The invention adopts the composite material composed of PAMAM dendrimer and nano metal oxide as the electron transport layer material, which can reduce the electron mobility of the quantum dot light-emitting diode, thereby balancing the electron hole injection rate of the quantum dot light-emitting diode and further improving the light-emitting efficiency of the quantum dot light-emitting diode. The mechanism for achieving the above effects is specifically as follows:
the PAMAM (polyamidoamine) dendrimer is both a sigma donor and a pi donor, which makes the PAMAM dendrimer have a certain electron transport ability, but since the PAMAM dendrimer itself does not have free electrons, its electron transport ability is weak compared to metal oxides. Compared with the nano metal oxide under the same condition, the electron mobility of the mixed material consisting of the PAMAM dendrimer and the nano metal oxide adopted by the invention is reduced, and the main reason is that the PAMAM dendrimer can effectively hinder the electron conduction capability of the nano metal oxide. Therefore, the mixed material composed of the PAMAM dendrimer and the nano metal oxide is used as the electron transport layer material of the quantum dot light-emitting diode, so that the electron mobility of the quantum dot light-emitting diode can be reduced, the electron hole injection rate of the quantum dot light-emitting diode is balanced, and the light-emitting efficiency of the quantum dot light-emitting diode is improved.
In a preferred embodiment, the PAMAM dendrimer is selected from one or more of the first generation PAMAM dendrimer (G1), the second generation PAMAM dendrimer (G2), the third generation PAMAM dendrimer (G3), the fourth generation PAMAM dendrimer (G4), the fifth generation PAMAM dendrimer (G5), the sixth generation PAMAM dendrimer (G6), the seventh generation PAMAM dendrimer (G7), the eighth generation PAMAM dendrimer (G8), the ninth generation PAMAM dendrimer (G9), and the tenth generation PAMAM dendrimer (G10), but is not limited thereto.
Specifically, the PAMAM (polyamide-amine) dendrimer is obtained by reacting different molecular units A (ethylenediamine) and B (methyl acrylate), and can be synthesized by a divergent method, in the first step, ethylenediamine and methyl acrylate react to generate carboxylic ester, in the second step, the obtained carboxylic ester reacts with excessive ethylenediamine, the first generation of PAMAM dendrimer can be obtained after the two steps of reactions, and the higher generation PAMAM dendrimer can be obtained by repeating the two steps of reactions. The PAMAM dendrimer with different generations contains the molecular units A and B with the general formulas: a (2)n+2n-1+…+2n -3)+B(2n+1+2n+….+2n-1) Wherein the value of n is 3-10; in addition, the first generation PAMAM dendrimer has a general formula a +4B for molecular unit a and molecular unit B, and the second generation PAMAM dendrimer has a general formula 5A +8B for molecular unit a and molecular unit B. As the generation number of PAMAM dendrimer becomes larger, the molecular volume thereof becomes larger and the intramolecular cavity thereof becomes larger, resulting in a corresponding decrease in the electron transport ability thereof. That is, the PAMAM dendrimer has a gradually decreased electron transport ability with the increase of generation, i.e., G1>G2>G3>G4>G5>G6>G7>G8>G9>G10。
Preferably, in this embodiment, PAMAM dendrimer molecules of different generations are mixed with the nano metal oxide to obtain a mixed material with different electron mobility, and the mixed material is used as an electron transport layer material of the quantum dot light emitting diode, so that the electron transport performance of the quantum dot light emitting diode can be adjusted, and thus the requirements of different devices can be met. By way of example, when an electron transport layer is prepared using a first generation PAMAM dendrimer with nano zinc oxide, its electron transport capability is greater than that of an electron transport layer prepared using a second generation PAMAM dendrimer with nano zinc oxide.
In a preferred embodiment, the nano metal oxide is selected from ZnO, NiO, W2O3、Mo2O3、TiO2、SnO、ZrO2And Ta2O3But is not limited thereto. Preferably, the particle size of the nano metal oxide is 1 to 20 nm.
More preferably, in the mixed material, the mass ratio of the PAMAM dendrimer to the nano metal oxide is 1-10: 10.
In a preferred embodiment, the invention further provides a trans-structured quantum dot light emitting diode, as shown in fig. 2, which includes a substrate 101, a cathode 102, an electron transport layer 103, a quantum dot light emitting layer 104, a hole transport layer 105, and an anode 106, which are stacked in sequence from bottom to top, wherein the electron transport layer is made of a mixed material composed of PAMAM dendrimer and nano metal oxide.
It should be noted that the invention is not limited to the quantum dot light emitting diode with the above structure, and may further include an interface functional layer or an interface modification layer, including but not limited to one or more of an electron blocking layer, a hole blocking layer, an electrode modification layer, and an isolation protection layer. The quantum dot light emitting diode can be partially packaged, fully packaged or not packaged.
Preferably, the material of the anode is selected from doped metal oxides; wherein the doped metal oxide includes, but is not limited to, one or more of indium-doped tin oxide (ITO), fluorine-doped tin oxide (FTO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide (IZO), magnesium-doped zinc oxide (MZO), and aluminum-doped magnesium oxide (AMO).
Preferably, the material of the hole transport layer is selected from organic materials having good hole transport ability, such as but not limited to Poly (9, 9-dioctylfluorene-CO-N- (4-butylphenyl) diphenylamine) (TFB), Polyvinylcarbazole (PVK), Poly (N, N 'bis (4-butylphenyl) -N, N' -bis (phenyl) benzidine) (Poly-TPD), Poly (9, 9-dioctylfluorene-CO-bis-N, N-phenyl-1, 4-Phenylenediamine) (PFB), 4', 4 "-tris (carbazol-9-yl) triphenylamine (TCTA), 4' -bis (9-Carbazole) Biphenyl (CBP), N '-diphenyl-N, N' -bis (3-methylphenyl) -1, one or more of 1 '-biphenyl-4, 4' -diamine (TPD), N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), doped graphene, undoped graphene, and C60.
Preferably, the material of the quantum dot light-emitting layer is selected from one or more of red quantum dots, green quantum dots and blue quantum dots, and can also be selected from yellow quantum dots. Specifically, the material of the quantum dot light emitting layer is selected from one or more of CdS, CdSe, CdTe, ZnO, ZnS, ZnSe, ZnTe, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InSb, AlAs, AlP, CuInS, CuInSe and various core-shell structure quantum dots or alloy structure quantum dots. The quantum dots of the present invention can be selected from cadmium-containing or cadmium-free quantum dots. The quantum dot light emitting layer of the material has the characteristics of wide and continuous excitation spectrum distribution, high emission spectrum stability and the like.
Preferably, the material of the cathode is selected from one or more of a conductive carbon material, a conductive metal oxide material and a metal material; wherein the conductive carbon material includes, but is not limited to, one or more of doped or undoped carbon nanotubes, doped or undoped graphene oxide, C60, graphite, carbon fibers, and porous carbon; the conductive metal oxide material includes, but is not limited to, one or more of ITO, FTO, ATO, and AZO; metallic materials include, but are not limited to, Al, Ag, Cu, Mo, Au, or alloys thereof; wherein, the metal material has a form including but not limited to one or more of a compact film, a nanowire, a nanosphere, a nanorod, a nanocone and a hollow nanosphere.
Further, the invention also provides a preparation method of the formal structure quantum dot light-emitting diode shown in fig. 1, wherein the preparation method comprises the following steps:
s10, providing an anode substrate;
s20, preparing a quantum dot light-emitting layer on the anode substrate;
s30, preparing an electron transport layer on the quantum dot light-emitting layer;
s40, preparing a cathode on the electron transport layer to obtain the quantum dot light-emitting diode, wherein the electron transport layer is made of a mixed material composed of PAMAM dendrimer and nano metal oxide.
Specifically, the quantum dot light emitting diode has a positive structure and an inversion structure. The positive structure comprises an anode, a cathode and a quantum dot light emitting layer, wherein the anode, the cathode and the quantum dot light emitting layer are arranged in a stacked mode, the anode of the positive structure is arranged on the substrate, hole function layers such as a hole transmission layer, a hole injection layer and an electron blocking layer can be further arranged between the anode and the quantum dot light emitting layer, and electronic function layers such as an electron transmission layer, an electron injection layer and a hole blocking layer can be further arranged between the cathode and the quantum dot light emitting layer. The reflection structure comprises an anode, a cathode and a quantum dot light emitting layer, wherein the anode and the cathode are arranged in a stacked mode, the quantum dot light emitting layer is arranged between the anode and the cathode, the cathode of the reflection structure is arranged on the substrate, hole function layers such as a hole transmission layer, a hole injection layer and an electron blocking layer can be further arranged between the anode and the quantum dot light emitting layer, and electronic function layers such as an electron transmission layer, an electron injection layer and a hole blocking layer can be further arranged between the cathode and the quantum dot light emitting layer.
For a positive type device, the bottom electrode disposed on the substrate is an anode, and in one embodiment of the present invention, the anode substrate may be a substrate on which the bottom electrode is disposed; in still another embodiment of the present invention, the anode substrate may include a substrate, a bottom electrode stacked on a surface of the substrate, and a hole transport layer stacked on the surface of the substrate; in still another embodiment of the present invention, the anode substrate may include a substrate, a bottom electrode stacked on a surface of the substrate, a hole injection layer stacked on the surface of the substrate, and a hole transport layer stacked on a surface of the hole injection layer; in still another embodiment of the present invention, the anode substrate may include a substrate, a bottom electrode stacked on a surface of the substrate, a hole injection layer stacked on the surface of the substrate, a hole transport layer stacked on a surface of the hole injection layer, and an electron blocking layer stacked on a surface of the hole transport layer.
For the inversion device, the bottom electrode disposed on the substrate is a cathode, and in one embodiment of the present invention, the cathode substrate may be a substrate on which the bottom electrode is disposed; in still another embodiment of the present invention, the substrate may include a substrate, a bottom electrode stacked on a surface of the substrate, and an electron injection layer stacked on the surface of the substrate.
The preparation method of each layer can be a chemical method or a physical method, wherein the chemical method comprises one or more of but not limited to a chemical vapor deposition method, a continuous ion layer adsorption and reaction method, an anodic oxidation method, an electrolytic deposition method and a coprecipitation method; physical methods include, but are not limited to, physical coating methods or solution methods, wherein solution methods include, but are not limited to, spin coating, printing, knife coating, dip-coating, dipping, spraying, roll coating, casting, slot coating, bar coating; physical coating methods include, but are not limited to, one or more of thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion coating, physical vapor deposition, atomic layer deposition, pulsed laser deposition.
In a preferred embodiment, the method for preparing the mixed material comprises the following steps: providing a PAMAM dendrimer; adding the PAMAM dendrimer and the nano metal oxide into a polar solvent according to the mass ratio of 1-10:10, mixing to obtain a colloidal solution, and drying the colloidal solution to obtain the mixed material.
In this embodiment, since the PAMAM dendrimer contains a large number of functional groups at the periphery thereof, and the functional groups have strong polarity and electronegativity, the PAMAM dendrimer has a good steric hindrance effect in a polar solvent, and agglomeration of the PAMAM dendrimer and the nano metal oxide after mixing in the polar solvent can be effectively avoided.
Preferably, the polar solvent is selected from one of water, ethanol and methanol, but is not limited thereto. More preferably, the polar solvent is ethanol.
Preferably, the concentration of PAMAM dendrimer in the colloidal solution prepared in this example is 10-40 mg/ml. Preferably, the concentration of the nano metal oxide is 20-80 mg/ml.
In a preferred embodiment, the nano metal oxide is selected from ZnO, NiO, W2O3、Mo2O3、TiO2、SnO、ZrO2And Ta2O3But is not limited thereto.
Preferably, the particle size of the nano metal oxide is 1 to 20 nm.
In a preferred embodiment, the colloid solution is prepared into a film by coating or printing, and is annealed to obtain the electron transport layer formed by the PAMAM dendrimer and the nano metal oxide. Because the PAMAM dendrimer has certain viscosity, the PAMAM dendrimer is mixed with the nano metal oxide to form a colloidal solution, which is favorable for film formation.
Preferably, after the colloid solution is prepared into a film, the film layer is annealed at the temperature of 60-150 ℃. More preferably, the annealing time is 15 to 60 min. Through the annealing treatment, an electron transport layer formed by the PAMAM dendrimer and the nano metal oxide can be prepared.
The PAMAM dendrimer is a sigma donor and a pi donor, so that the PAMAM dendrimer has certain electron transport capacity, but the PAMAM dendrimer does not have free electrons per se, so that the electron transport capacity of the PAMAM dendrimer is weaker than that of a metal oxide. The mixed material composed of PAMAM dendrimer and nano metal oxide is used as the electron transport layer material of the quantum dot light-emitting diode, so that the electron mobility of the quantum dot light-emitting diode can be reduced, the electron hole injection rate of the quantum dot light-emitting diode is balanced, and the light-emitting efficiency of the quantum dot light-emitting diode is improved.
The invention also provides a preparation method of the trans-structure QLED containing the hole transport layer, which comprises the following steps:
providing a substrate;
preparing a cathode on the substrate;
preparing an electron transport layer on the cathode, wherein the electron transport layer is made of a mixed material consisting of PAMAM dendrimer and nano metal oxide;
preparing a quantum dot light-emitting layer on the electron transport layer;
preparing a hole transport layer on the quantum dot light emitting layer;
and preparing an anode on the hole transport layer to obtain the QLED.
The preparation method of each layer can be a chemical method or a physical method, wherein the chemical method comprises one or more of but not limited to a chemical vapor deposition method, a continuous ion layer adsorption and reaction method, an anodic oxidation method, an electrolytic deposition method and a coprecipitation method; physical methods include, but are not limited to, physical coating methods or solution methods, wherein solution methods include, but are not limited to, spin coating, printing, knife coating, dip-coating, dipping, spraying, roll coating, casting, slot coating, bar coating; physical coating methods include, but are not limited to, one or more of thermal evaporation coating, electron beam evaporation coating, magnetron sputtering, multi-arc ion coating, physical vapor deposition, atomic layer deposition, pulsed laser deposition.
The quantum dot light emitting diode and the method for manufacturing the same according to the present invention will be described in detail by examples below:
example 1
The quantum dot light-emitting diode comprises an anode substrate, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer and a cathode which are arranged in a laminated mode from bottom to top, wherein the electron transport layer is made of a mixed material composed of a fifth generation PAMAM dendrimer and nano zinc oxide. The preparation method of the quantum dot light-emitting diode comprises the following steps:
1) and preparing nano zinc oxide: dispersing 0.5mol of hydrated zinc acetate in 25ml of dimethyl sulfoxide to completely disperse the hydrated zinc acetate, dispersing 0.55mol of tetramethyl ammonium hydroxide in 30ml of ethanol to completely disperse the hydrated zinc acetate, mixing and stirring the two mixed solutions at room temperature for 1 hour, and performing centrifugal cleaning to obtain nano zinc oxide;
2) preparation of colloidal solution: adding 20mg of the fifth generation PAMAM dendrimer and 50mg of nano zinc oxide into 1ml of ethanol, and mixing to prepare a colloidal solution;
3) and preparing the quantum dot light-emitting diode:
spin-coating PVK on a cleaned ITO glass sheet at the rotating speed of 4000rpm for 60s, and then annealing at 150 ℃ for 15min to prepare a hole transport layer;
spin-coating a red quantum dot CdSe/ZnS solution on the hole transport layer at the rotating speed of 2000rpm for 60s to prepare a quantum dot light-emitting layer;
spin-coating the colloidal solution prepared in the step 2) on the quantum dot light-emitting layer at the rotating speed of 3000rpm for 60s, and then annealing at 120 ℃ for 30min to prepare an electron transmission layer;
and finally, depositing a 150nm aluminum electrode on the electron transmission layer by a mask plate in a thermal evaporation mode to obtain the quantum dot light-emitting diode.
Example 2
A quantum dot light-emitting diode comprises an anode substrate, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer and a cathode which are arranged in a laminated mode from bottom to top, wherein the electron transport layer is made of a mixed material composed of second-generation PAMAM dendrimer and nano nickel oxide. The preparation method of the quantum dot light-emitting diode comprises the following steps:
1) and preparing nano nickel oxide: dispersing 0.5mol of hydrated nickel acetate in 25ml of dimethyl sulfoxide to completely disperse the hydrated nickel acetate, dispersing 0.55mol of tetramethyl ammonium hydroxide in 30ml of ethanol to completely disperse the hydrated nickel acetate, mixing and stirring the two mixed solutions at room temperature for 1 hour, and performing centrifugal cleaning to obtain nano nickel oxide;
2) preparation of colloidal solution: adding 30mg of second generation PAMAM dendrimer and 70mg of nano nickel oxide into 1ml of ethanol, and mixing to prepare a colloidal solution;
3) and preparing the quantum dot light-emitting diode:
spin-coating TFB on a cleaned ITO glass sheet at the rotating speed of 4000rpm for 60s, and then annealing at 150 ℃ for 15min to prepare a hole transport layer;
spin-coating a red quantum dot CdSe/ZnS solution on the hole transport layer at the rotating speed of 2000rpm for 60s to prepare a quantum dot light-emitting layer;
spin-coating the colloidal solution prepared in the step 2) on the quantum dot light-emitting layer at the rotating speed of 3000rpm for 60s, and then annealing at 100 ℃ for 40min to prepare an electron transmission layer;
and finally, depositing a 100nm aluminum electrode on the electron transmission layer by a mask plate in a thermal evaporation mode to obtain the quantum dot light-emitting diode.
Example 3
The quantum dot light-emitting diode comprises an anode substrate, a hole transport layer, a quantum dot light-emitting layer, an electron transport layer and a cathode which are arranged in a laminated mode from bottom to top, wherein the electron transport layer is a mixed material composed of first generation PAMAM dendrimer, fourth generation PAMAM dendrimer and nano nickel oxide. The preparation method of the quantum dot light-emitting diode comprises the following steps:
1) and preparing nano nickel oxide: dispersing 0.5mol of hydrated nickel acetate in 25ml of dimethyl sulfoxide to completely disperse the hydrated nickel acetate, dispersing 0.55mol of tetramethyl ammonium hydroxide in 30ml of ethanol to completely disperse the hydrated nickel acetate, mixing and stirring the two mixed solutions at room temperature for 1 hour, and performing centrifugal cleaning to obtain nano nickel oxide;
2) preparation of colloidal solution: adding 10mg of first generation PAMAM dendrimer, 20mg of fourth generation PAMAM dendrimer and 60mg of nano nickel oxide into 1ml of ethanol, and mixing to prepare a colloidal solution;
3) and preparing the quantum dot light-emitting diode:
spin-coating TFB on a cleaned ITO glass sheet at the rotating speed of 4000rpm for 60s, and then annealing at 150 ℃ for 15min to prepare a hole transport layer;
spin-coating a red quantum dot CdSe/ZnS solution on the hole transport layer at the rotating speed of 2000rpm for 60s to prepare a quantum dot light-emitting layer;
spin-coating the colloidal solution prepared in the step 2) on the quantum dot light-emitting layer at the rotating speed of 3000rpm for 60s, and then annealing at 100 ℃ for 40min to prepare an electron transmission layer;
and finally, depositing a 100nm aluminum electrode on the electron transmission layer by a mask plate in a thermal evaporation mode to obtain the quantum dot light-emitting diode.
In summary, the quantum dot light emitting diode provided by the invention includes an electron transport layer, and the electron transport layer is made of a mixed material composed of PAMAM dendrimer and nano metal oxide. The PAMAM dendrimer is a sigma donor and a pi donor, so that the PAMAM dendrimer has certain electron transport capacity, but the PAMAM dendrimer does not have free electrons per se, so that the electron transport capacity of the PAMAM dendrimer is weaker than that of a metal oxide. The mixed material composed of PAMAM dendrimer and nano metal oxide is used as the electron transport layer material, so that the electron mobility of the quantum dot light-emitting diode can be reduced, the electron hole injection rate of the quantum dot light-emitting diode is balanced, and the light-emitting efficiency of the quantum dot light-emitting diode is improved.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (8)
1. A quantum dot light-emitting diode comprises a cathode, an anode and a quantum dot light-emitting layer arranged between the cathode and the anode, wherein an electron transport layer is arranged between the cathode and the quantum dot light-emitting layer, and is characterized in that the electron transport layer is made of a mixed material composed of PAMAM dendrimer and nano metal oxide, the PAMAM dendrimer is selected from one or more of first-generation to tenth-generation PAMAM dendrimers, and the mass ratio of the PAMAM dendrimer to the nano metal oxide is 1-10: 10.
2. The quantum dot light-emitting diode of claim 1, wherein the nano metal oxide is selected from ZnO, NiO, W2O3、Mo2O3、TiO2、SnO、ZrO2And Ta2O3One or more of (a).
3. The quantum dot light-emitting diode of claim 1, wherein the nano metal oxide has a particle size of 1 to 20 nm.
4. A preparation method of a quantum dot light-emitting diode is characterized by comprising the following steps:
providing an anode substrate, preparing a quantum dot light-emitting layer on the anode substrate, preparing an electron transport layer on the quantum dot light-emitting layer, and preparing a cathode on the electron transport layer to prepare the quantum dot light-emitting diode;
or, providing a cathode substrate, preparing an electron transport layer on the cathode substrate, preparing a quantum dot light-emitting layer on the electron transport layer, and preparing an anode on the quantum dot light-emitting layer to obtain the quantum dot light-emitting diode;
the electron transport layer is made of a mixed material composed of PAMAM dendrimer and nano metal oxide, the PAMAM dendrimer is selected from one or more of first-generation to tenth-generation PAMAM dendrimers, and the mass ratio of the PAMAM dendrimer to the nano metal oxide is 1-10: 10.
5. The method for preparing the quantum dot light-emitting diode of claim 4, wherein the method for preparing the mixed material comprises the following steps:
providing a PAMAM dendrimer;
adding the PAMAM dendrimer and the nano metal oxide into a polar solvent according to the mass ratio of 1-10:10, mixing to obtain a colloidal solution, and drying the colloidal solution to obtain the mixed material.
6. The method for preparing the quantum dot light-emitting diode of claim 5, wherein the concentration of PAMAM dendrimer in the colloidal solution is 10-40 mg/ml; and/or the concentration of the nano metal oxide is 20-80 mg/ml.
7. The method of claim 5, wherein the step of preparing an electron transport layer on the quantum dot light emitting layer comprises: depositing the colloidal solution on the quantum dot light-emitting layer, and annealing to form an electron transmission layer;
alternatively, the step of preparing an electron transport layer on the cathode substrate comprises: and depositing the colloidal solution on the cathode substrate, and annealing to form an electron transport layer.
8. The method for preparing the quantum dot light-emitting diode according to claim 7, wherein in the annealing treatment step, the annealing temperature is 60-150 ℃; and/or the annealing time is 15-60 min.
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